Benzidine rearrangements. 17. The concerted nature of the one-proton p-semidine rearrangement of 4-methoxyhydrazobenzene

Autor:	Henry J. Shine, Ann Gafney Horgan, Martin W. Brechbiel, Henryk Zmuda, Harold Kwart
Rok vydání:	1982
Předmět:	Aqueous solution Proton Chemistry Inorganic chemistry chemistry.chemical_element General Chemistry Kinetic energy Biochemistry Nitrogen Medicinal chemistry Catalysis Benzidine chemistry.chemical_compound Colloid and Surface Chemistry Kinetic isotope effect Carbon
Zdroj:	Journal of the American Chemical Society. 104:5181-5184
ISSN:	1520-5126 0002-7863
Popis:	The nitrogen kinetic isotope effects (KIE) for the acid-catalyzed rearrangement of 4-methoxyhydrazobenzene (1b) into the p-semidine (4-methoxy-4'-aminodiphenylamine, 2b) and o-semidine(2-amino-5-methoxydiphenylamine, 3b) have been measured and are 1.0296 (av) and 1.074 (av), respectively. The carbon KIE for formation of 2b was found to be 1.039 (av). The results show that p-semidine formation is a concerted process. Rearrangements were carried out in 60% aqueous dioxane under conditions of earlier kinetic work. Mixtures of 1b and (/sup 15/N, /sup 15/N')1b were used for the nitrogen KIE, measured mass spectrometrically with isolated N-benzoyl-2b, and mixtures of 1b and (4'-/sup 14/C)1b for the carbon KIE, measured with scintillation counting on isolated N-benzoyl-2b. The method of carbon labeling did not allow for a measurement of the KIE for formation of 3b.
Databáze:	OpenAIRE
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